Drilling fluids



United States Patent 3,346,489 DRILLING FLUIDS 1 Woodrow J. Dickson, La Habra, and Fred W. Jenkins, Buena Park, Calif., assiguors to Petrolite Corporation No drawing. Application May 24, 1965, Ser. No. 458,373, which is a continuation of application Ser. No. 115,883, June 9, 1961, and is also a division of application Ser. No. 47,387, Aug. 4, 1960. Divided and this application Mar. 4, 1966, Ser. No. 531,795

3 Claims. (Cl. 252-85) This application is a division of application Ser. No. 47,387, filed on Aug. 4, 1960, now abandoned, and is copending with application Ser. No. 458,373, filed on May 24, 1965, as a division of said application Ser. No. 458,373, which has become abandoned, and is also a continuation of application Ser. No. 115,883, filed on June 9, 1961, now abandoned, and is copending with each of the following applications:

Ser. No. 1. 505,037 2. 115,876

Filing Date Oct. 24, 1965 June 9, 1961 3. 505,039 Oct.24, 1965 4. 115,877 Iune9,1961

5. 115,878 June9,1961

6. 115,881 June9, 196l 7. 115,882 June9, 1961 8., 115,884 June9,1961

Sept. 11, 1963 This invention relates to polyalkyleneimines and to derivatives thereof. More particularly, this invention relates to polyethyleneimine and to polyethyleneimine derivatives containing various groups, such as the oxyalkylated, acylated, alkylated, carbonylated, olefinated, etc., derivatives thereof, prepared by introducing such groups individually, alternately, in combination, etc., including for example, derivatives prepared by varying the order of adding such groups, by increasing the number and order of adding such groups, and the like.

This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers for water-in-oil emul sions; as demulsifiers for oil-in-water emulsions; as corrosion inhibitors; as fuel oil additives for gasoline, diesel fuel, jet fuel, and the like; as lubricating oil additives; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as antioxidants, gasoline stabilizers, fungicides, etc.; as flotation agents, for example, as flotation collection agents; as asphalt additives or anti-stripping agents for asphaltmineral aggregate compositions; as additives for compositions useful in acidizing calcareous stratas of oil wells; as additives for treating water used in the secondary recovery of oil and in disposal wells; as additives'used in ice treating oil-well strata in primary oil recovery to enhance the flow of oil; as emulsifiers for both oil-in-water and Water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for oil to prevent emulsification during transport; as additives for drilling muds; as agents useful in removing mud sheaths from newly drilled wells; as dehazing or fog-inhibiting agents for fuels; as additives for preparing sand or mineral slurries useful in treating oil wells to enhance the recovery of oil; as agents for producing polymeric emulsions useful in preparing water-vapor impermeable paper board; as agents in parafiin solvents; as agents in preparing thickened silica aerogel lubricants; as gasoline additives to remove copper therefrom; as deicing and anti-stalling agents for gasoline; as antiseptic, preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agents for the textile industry, for example, as mercerizing assistants, as wetting agents, as rewetting agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing assistants, as anti-static agents, and the like; as additives for rubber latices; as entraining agents for concrete and cements; as anti-static agents for rugs, floors, upholstery, plastic and Wax polishes, textiles, etc; as detergents useful :in metal cleaners, in floor oils, in dry cleaning, in general cleaning, and the like; as agents useful in leather processes such as in fiat liquoring, pickling, acid degreasing, dye fixing, and the like; as agents in metal pickling; as additives in paints for improved adhesion of primers, in preventing waterspotting in lacquer; as anti-Skinners for pigment flushing, grinding and dispersing, as antifeathering agents in ink; as agents in the preparation of Wood pulp and pulp slurries, as emulsifiers for insecticidal compositions and agricultural sprays such as DDT, 24-D (toxaphene), chlordane, nicotine sulfate, hexachlorocyclohexane, and the like; as agents useful in building materials, for example, in the water repellent treatment of plaster, concrete, cement, roofing materials, floor sealers; as additives in bonding agents for various insulating building materials; and the like. I

Polyalkyleneimine employed in this invention include high molecular weight polyethyleneimine, i.e. polymers of ethyleneimine,

' CHg-CH or substituted products thereof:

etc., wherein R, R and R" are hydrogen or a substituted group, for example a hydrocarbon group such as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, etc., but preferably hydrogen or alkyl.

Thus, polyethyleneimine is polymerized, substituted or an unsubstituted, 1,2-alkyleneimine. Although polyethyleneimine is the preferred embodiment, other illustrative examples include, for example,

CHC H:

1,2-propy1eneimine CH-C 1H CH 1,2-butyleueimine CH-C H:

CH-OH:

2,3-butyleneimine 'C-butylethyleneimine Gil-012 25 CH2 C-dodecylethyleneimine CH-CIBHS'I V CHa C-octadecylethyleneimine A preferred class of polymerized 1,2-alkyleneimines include those derived from polymerizing RCH-R'CH H wherein R and R are hydrogen or an alkyl radical, the latter being the same or different. Of the substituted ethyleneimines, propyleneimines are preferred.

The polyethyleneimines useful herein have molecular weights of, for example, at least 800, for example from 800 to 100,000 or higher, but preferably 20,000 to 75,000 or higher. There is no upper limit to the molecular weight of the polymer employed herein and molecular weights of 200,000, 500,000 or 1,000,000 or more can be employed.

The optimum molecular weight will depend on the particular derivative, the particular use, etc.

Although these products are generally prepared by polymerizing 1,2-alkyleneimines, they may also be prepared by other known methods, for example, by decarboxylating 2-oxazolidine as described in 2,806,839, etc.

Commercial examples of these compounds are available, for example, those sold by the Chemirad Corporation as PEI in a 50% by weight aqueous solution having a molecular weight of 3040,000. Propyleneimine is also commercially available and suitable polymers can be prepared from this material.

For convenience and simplicity, this invention will be illustrated by employing polyethyleneimine.

Polyethyleneimine is a well known polymer whose preparation from ethyleneimine is described in US. Patent 2,182,306 and elsewhere. For convenience in polymerizing and handling, the polymer is generally prepared as .an aqueous solution. Water can be removed, if desired, by .distilling the water therefrom or by azeotroping the water therefrom in the presence of a hydrocarbon, such .as xylene, and using the solution and/or suspension obtained thereby for further reaction or use. The following polyethyleneimines of the molecular weights indicated are employed herein to illustrate this invention.

Polymer designation: Approx. mol. wt. range Polyethyleneimine 4 ACYLATION A wide variety of acylating agents can be employed. Acylation is carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.

The temperature at which reaction between the acylating agent and polyethyleneimine is effected is not too critical a factor. Since the reaction involved appear to be an amide-formation reaction and a condensation reaction, the general temperature conditions for such reactions, which are well known to those skilled in the art, are applicable.

Acylation is conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from to 280 C., but preferably at to 200 C.

The product formed on acylation will vary with the particular conditions employed. First the salt, then the amide is formed. If, however, after forming the amide at a temperature between 140-250 C., but usually not above 200 0., one heats such products at a higher range, approximately 250-280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid group employed, the first mole of water being evolved during amidification. The product formed in such cases contains a cyclic amidine ring, such as an imidazoline or a tetrahydropyrimidine ring. Infrared analysis is a convenient method of determining the presence of these groups.

Water is formed as a by-pr-oduct of the reaction between the acylating agent and polyethyleneimine. In order to facilitate the removal of this water, to effect a more complete reaction in accordance with the principle of LeChatelier, a hydrocarbon solvent which forms an azeotropic mixture with water can be added to the reaction mixture. Heating is continued with the liquid reaction mixture at the preferred reaction temperature, until the removal of water by azeotropic distillation has substantially ceased. In general, any hydrocarbon solvent which forms an azeotropic mixture with water can be used. It is preferred, however, to use an aromatic hydrocarbon solvent of the benzene series. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and the reaction temperature selected. Accordingly, a sutficient amount of solvent must be used to support the azeotropic distillation, but a large excess must be avoided since the reaction temperature will be lowered thereby. Water produced by the reaction can also be removed by operating under reduced pressure. When operating with a reaction vessel equipped with a reflux condenser provided with a water takeoff trap, sufiicient reduced pressure can be achieved by applying a slight vacuum to the upper end of the condenser. The pressure inside the system is usually reduced to between about 50 and about 300 millimeters. If desired, the water can be removed also by distillation, while operating under relatively high temperature conditions.

The time of reaction between the acylating agent and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the water from the reaction mixture. In practice, the reaction is continued until the formation of water has substantially ceased. In general, the time of reaction will vary between about 4 hours and about ten hours.

Although a wide variety of carboxylic acids produce excellent products, carboxylic acids having more than six carbon atoms and less than 40 carbon atoms but preferably 8-30 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturallyoccurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are ditferent in structure, but can be included in the broad generic term previously indicated.

Suitable acids .include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, 'fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, .eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, anglic, teglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octeno'ic acids, the nonenoic acids, thedecenoic acids, for example, obtusilic acid, the undecenoicacids, the dodecenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid,-the heptadeceno'ic acids, the octodeeenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoicacids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudo eleostearic acid, and the like.

Carboxylic acids containingiunctional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, th e'hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxy-myristic acids, the hydroxypentadecanoic acids, the hydroxypalmitio acids, the hydroxyhexa-decanoic acids, the hydroxyheptadecanoic acids, the hydroxy stear'ic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylatedhydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, choroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarbic and chaumoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fenchloli c acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic'acids, for example, the toluic acids, the xyleneic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil,

cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, mont-an wax, Japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyll-astearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraflin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc. I

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocenic, citraconic, glutonic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acid, terepht-halic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric, and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery -Industries,'and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acid halides, glycerides, etc., can be employed in place of the 'free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the correspond ing acid is utilizable for the production of the reaction products of the present invention. The general structural formulae of these compounds are:

Anhydri de RCHO wherein R is an alkenyl radical. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated'at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvi-v oils, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. Although their use is less desirable, the alkenyl succinic acids also react, in accordance with this invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side reactions to occur to some extent. Nevertheless, the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term alkenyl succinic acid anhydride, is used herein, it must be clearly understood that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated as set forth hereinbefore. Non-limiting examples of the alkenyl succinic acid anhydride reactant are:

ethenyl succinic acid anhydrides;

ethenyl succinic acid;

ethyl succinic acid anhydride;

propenyl succinic acid anhydride;

sulfurized propenyl succinic acid anhydride; butenyl succinic acid;

2-methylbutenyl succinic acid anhydride; 'l,2-dichloropentyl succinic acid anhydride;

hexenyl succinic acid anhydride;

hexyl succinic acid;

sulfurized 3-methy1pentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-2-ethylbutyl succinic acid;

heptenyl succinic acid anhydride;

1,2-diiodooctyl succinic acid;

octenyl succinic acid anhydride;

Z-methyl-heptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid;

2-isopropylpentenyl succinic acid anhydride; noneyl succinic acid anhydride;

2-propylhexenyl succinic acid anhydride;

decenyl succinic acid;

decenyl succinic acid anhydride; 5-methyl-2-isopropylhexenyl succinic acid anhydride; 1,2-dibromo-2-et-hyloctenyl succinic acid anhydride; decyl succinic acid anhydride;

undecenyl succinic acid anhydride; l,2-dichloro-undecyl succinic acid anhydride; .1,2-dichloro-undecyl succinic acid; 3-ethyl-2-t-butylpentenyl succinic acid anhydride; dodecenyl succinic acid anhydride;

dodecenyl succinic acid;

2-propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acid anhydride;

tridecenyl succinic acid anhydride;

tetradecenyl succinic acid anhydride;

hexadecenyl succinic acid anhydride;

sulfurized octadecenyl succinic acid;

octadecyl succinic acid anhydride; 1,2-dibrom-Z-methylpentadecenyl succinic acid anhydride; 8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,Z-dichloro-2-methylnonadeceny1succinic acid anhydride; 2-octyldodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid;

hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are difficult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are utilizable herein.

In summary, without any intent of limiting the scope of the invention, acylation includes amidification, the formation of the cyclic amidine ring, the formation of acid imides such as might occur when anhydrides such as the alkenylsuccinic acids are reacted, i.e.

0 RGH-i J N-P H -CJ wherein P=the polyethyleneimine residue, polymers as might occur when a dicarboxylic acid is reacted intermolecularly with polyethyleneimine, cyclization as might occur when a dicarboxylic acid reacts intramolecularly with polyethyleneimine as contrasted to intermolecular reactions, etc. The reaction products may contain other substances. Accordingly, these reaction products are most accurately defined by a definition comprising a recitation of the process by which they are produced, i.e., by acylation.

The moles of acylating agent reacted with polyethyleneimine will depend on the number of acylation reactive positions contained therein as well as the number of moles of acylating agent one wishes to incorporate into the polymer. Theoretically one mole of acylating agent can be reacted per amino group on the polyethyleneimine molecule. We have advantageously reacted 1-20 moles of acylating agent per mole of polyethylene 900, but preferably l-12 moles. Proportionately greater amounts of acylating agent can be employed with polyethyleneimine of higher molecular weight. Thus, with polyethyleneimine 20,000, l50 moles of acylating agent can be employed, and with polyethyleneimine 35,000, 1-ll00 moles can be employed, etc. Optimum acylation will depend on the particular use.

The following examples are illustrative of the preparation of the acylated polyethyleneimine.

The following general procedure is employed in acylating. A xylene suspension of polyethyleneimine, after the removal of water, is mixed with the desired ratio of acid. Heat is then applied. After the removal of the calculated amount of water (1 to 2 equivalents per carboxylic acid group of the acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from to 200 C. Where the formation of the cyclic amidine type structure is desired, the maximum temperature is generally 180- 250 C. and more than one mole of water per carboxylic group is removed. The reaction times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 1A- The reaction is carried out in a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle to 1 mole (900 grams) of polyethyleneimine 900 in an equal weight of xylene (i.e., 900 grams), 200 grams of lauric acid (1 mole) is added with stirring in about ten minutes. The reaction mixture is then heated gradually to about C. in half an hour and then held at about C. over a period of 3 hours until 19 grams (1.1 moles) of water is collected in the side of the tube. The solvent is then removed with gentle heating under reduced pressure of approximately 20 mm. The product is a dark, viscous, xylene-soluble liquid.

Example 1A grams (2 moles) of water are removed instead of 19 grams (1.1 moles). Infrared analysis of the product indicates the presence of a cyclic amidine ring.

The following examples of acylated polyethyleneimines are prepared in the manner of the above examples from the polyethyleneimine noted in the following table. The products obtained are dark, viscous materials.

In the examples the symbol A identifies the acylated polyethyleneimine. Thus, specifically 1-A, represents acylated polyethyleneimine.

TABLE I.AC-YLATED TRIQIIIDJDQTEEJTS OF POLYETHYLENEI- Molecular weight of polyethyleneimine Ratio mols of Water removed per mol of acid Ratio mols of acid per mol of PE Acid o Dimeric (600) (Emery ustries) o Nonanoic (158) do. Alkenyl (Cu) Su Anhy. (266). do do Naphthenic (330) (Sunapic Acid B). Maleic Anhydride (98).

' Diphenolic. (286) The following table presents specific illustration of com-- pounds other than polyethyleneimine and its derivatives.

TABLE I A.ACYLATED PRODUCTS OF POLYPROPYLENEIMINE Molecular Weight of Polypropyleneimine Mols of Acid per Acid Mol of Polypropylenermme Alkenyl (C12) S Anhydride (266).-

, 10 OXYALKYLATION Polyethyleneirnine can be oxyalkylated in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions of propylene oxide and ethylene oxide, or smaller proportions thereof in relation to polyethyleneimine. Thus, the molar ratio of alkylene oxide to polyethyleneimine can range Within Wide limits, for example, from a 1:1 mole ratio to a ratio of 1000:1, or higher, but preferably 1 to 200. For example, in demulsification extremely high alkylene oxide ratios are often advantageously employed such as 200-300 or more moles of alkylene oxide per mole of polyethyleneimine. On the other hand, for certain applications such as corrosion prevention and use as fuel oil additives, lower ratios of alkylene oxides are advantageously employed, i.e'., 1-10/25 moles of alkylene oxide per mole of polyethyleneimine. With higher molecular weight polyethyleneimine, more oxyalkylatable reaction centers are preseat for alkylene oxide addition and very high ratios of alkylene oxide can be added. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation re actions are conducted under a wide variety of conditions,

at low or high pressures, at low or high temperatures, in

the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 200 C., and pressures of from 10 to 200 p.s.i., and times of from 15 min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 p.s.i. For conditions of oxyalkylation reactions see US. Patent 2,792,369 and other patents mentioned therein. 1

oxyalkylation is too well known to require a full dis,- cussion. For purpose of brevity reference is made to Parts 1 and 2 of US. Patent No. 2,792,371, dated May 14, 1957, to Dickson in which particular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The symbol employed to designate oxyalkylation is O. Specifically 1 O represents oxyalkylated polyethyleneimine.

In the following oxyalkylations the reaction vessel employed is a stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means and the like which are conventional in this type of apparatus. The stirrer is operated at a s'peed of 250 rpm. Polyethyleneimine dissolved and/ or suspended in an equal weight of xylene is charged into the reactor. The autoclave is sealed, swept with nitrogen, stirring started immediately and heat applied. The temperature is allowed to rise to approximately C. at which time the addition of the alkylene oxide is started and added continuously at such speed as it is absorbed by the reaction mixture. When the rate of oxyalkylation slows down appreciably, which generally occurs after about 15 moles of ethylene oxide are added or after about 10 moles of propylene oxide are added, the reaction vessel is opened and an oxyalkylation catalyst is added (in 2 weight per cent of the total reactants present). The catalyst employed in the examples is sodium methylate. Thereupon the autoclave is flushed out as before and oxyalkylation completed. In the case of oxybutylation, oxyoctylation, oxystyrena- 11 tion, and other oxyalkylations, etc., the catalyst is added at the beginning of the operation.

Example 1-0 Using the oxyalkylation apparatus and procedure stated above, the following compounds are prepared: 900 grams (1 mol) of polyethyleneimine 900 in xylene are charged into a stainless steel autoclave, swept with nitrogen, stirring started, and autoclave sealed. The temperature is allowed to rise approximately 100 C. and ethylene oxide is injected continuously until 220 grams (5 mols) total had been added over a one-half hour period. This reaction is exothermic and requires cooling to avoid a rise in temperature after removal of xylene. The reaction mass is transferred to a suitable container. Upon cooling to room temperature, the reaction mass is a dark extremely viscous liquid.

Example 1-0 The same procedure as Example 1-0 is used except that 396 grams of ethylene oxide (9 mols) is added to 900 grams (1 mol) of polyethyleneimine 900. This reaction material is a dark viscous liquid at room temperature.

Example 1-O The same procedure as Example 1-0 is used and 396 grams of ethylene oxide (9 mols) are added to 900 grams (1 mol) of polyethyleneimine 900. After this reaction is completed, the autoclave is opened and 20 grams of sodium methylate are added. The autoclave is then flushed again with nitrogen and an additional 572 grams (13 mols) of ethylene oxide is added at 100 C. This reaction is highly exothermic. The reaction mass now contains 1 mol of polyethyleneimine 900 and a total of 22 mols of reacted ethylene oxide.

Example 1-O A portion of the reaction mass of Example 1-O is transferred to another autoclave and an additional amount of EtO was added. The reaction mass now contains the ratio of 1 mol of polyethyleneimine 900 to 40 mols of EtO.

Example 1-0,;

The addition of ethylene oxide to Example 1-0., is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 75 mols of E is reached.

Example 1-0 The addition of ethylene oxide to Example lO is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 83 mols of EtO is reached.

Example 1-07 The addition of ethylene oxide to the Example 1-0 is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 105 mols of EtO is reached.

Example 16-0 2,000 grams (0.1 mol) of polyethyleneimine of molecular weight of 20,000 in xylene are charged into a conventional stainless steel autoclave. The temperature is raised to 120 C., the autoclave is flushed with nitrogen and sealed. Then 11.6 grams of propylene oxide (0.2 mol) are added slowly at 120 C. A sample is taken at this point and labeled 16-0 This sample contains two mols of PrO for each mol of polyethyleneimine. It is a dark, pasty solid at room temperature.

Example 16-0 The addition of propylene oxide to 16-0 is continued as follows: The autoclave is opened and 5 grams of sodium methylate are added. The autoclave is again purged with nitrogen and sealed. Propylene oxide is added carefully until an additional 23.2 grams have been reacted. A sample is taken at this point and labeled l6O This 12 compound now contains 6 mols of propylene oxide for each mol of polyethyleneimine 20,000.

Example 16-0 The oxypropylation of 16-0 is continued until an additional 52.2 grams of propylene oxide are reacted. A sample is taken at this point and labeled 16-0 16-0 contains 15 mols of propylene oxide for each mol of polyethyleneimine 20,000. At room temperature the product is a dark, pasty solid.

This oxyalkylation is continued to produce Examples 16-0- 16O A summary of oxyalkylated products produced from polyethyleneimines is presented in the following Table II.

The Roman numerals (I), (II), and (III) beside the moles of oxide added indicate the order of oxide addition (I) first, (II) second and (III) third, etc.

The following abbreviations are also used throughout this application:

EtOEthylene oxide Pro-Propylene oxide BuO--Butylene oxide TABLE II.OXYALKYLATED PRODUCTS [Mols of alkylene oxide /1uol polyethyleneimine] Ex. Mol. Wt. EtO PrO BuO Physical properties of PE l-Oi 900 Viscous liquid. 1-02. 900 Solid. 1-0 900 Do. 1-04- 900 Do. 1-05. 900 Do. l-Os 900 Do. 1O1. 900 D0. 1-03. 900 D0. 2-01- 900 Viscous liquid. Z-Oz. 900 D0. 2-0 900 Dark, thick liquid. 2-04- 900 Do. 2-05. 900 Do. 2-0a. 900 D0. 2-Ov- 900 D0. Z-Os 900 Do. 3-01. 900 Do. 3-01. 900 D0. 3-03- 900 Do. 3-04 900 D0. 4-01- 900 Viscous liquid. 4-02- 900 D0. 4-03. 900 Solid. 4-04 900 Do. 5-01- 900 Viscous liquid. 6-01- 900 Dark, thick liquid. G-Oz. 900 D0. 6-0: 900 D0. 6-04. 900 20 (I) (II) 5 (III) D0. 7-0 900 Octylene oxide, 8 mols Viscous liquid. 8-0 900 Styrene oxide, 5 mols Do. 9-0 900 Epoxide 201 (Carbide and Solid.

Carbon), 1 mol 10-01 Viscous liquid. 10-02.. D0. 10-03 Solid. 10-04. D0. 10-05 DO- 10-0e D0. 11-0 1 Viscous liquid. 11-0i.. Dark, thick liquid. 11Oa.. D0. 11-04 D0. 11-05. D0. IZ-OL. DO. 12-02.. D0. 12-Oa.- D0. 12-O4.. D0. 13-01.. Viscous liquid. 13-02 Solid. 13-03.. D0. 13-04.. DO. 14-01-. Viscous liquid. 14-02.. D0. 14-03.. DO. 14-04.. Solid. 14-05.. 0 15 (I) 2 Viscous liquid. 14-00.. 5,000 6 (III) 3 (I) 2 (II) Do. 15-01.. 20, 000 10 15-02.- 20, 000 35 15-03.- 20, 000 60 15-04 20, 000 85 15-05 20,000 15-05 20, 000

TABLE II.Continued w 7 TABLE IIACntinued Ex. M01. Wt. EtO PrO BuO Physical properties M01. f Mols'of alkylene oxide per Physicgl Dark, pasty solid. Ex 3 ol of polypropyleneimme properties pyleneimine EtO PrO BuO Pastysolids1 0, 500 12 (II) 44 1 Thick dark liquid.

32-01" 500 5(II' 10 (II) 10 (I) Do.

Llght brown Sond- 33-0- v 500 Octylene oxide, mols Do.

34-0 500 Styrene oxide, 3 mols D0. 35 o 50o Epoxide 201 (Carbide and Solid.

Carbon), 1 mol 36 O1 1, 000

Hlb aze:

J-rrrrrr QQOOSOO CDDOO 00 00000008 2 (I 8 (I) Solid.

10 (1H) 10 (I) Thick liquid.

Epoxide 201 (Carbide and Solid.

Carbon) 2 mols Styrene oxide, 6 mols Viscous liquid. Octylene oxide, 2 mols 0.

Do: Viscous liquid. Thick liquid.

The following table presents specific illustration of compounds other than polyethyleneimine and its deriv- .O3.- atives. 5001-.

.TABLE IIA.OXYALKYLATED-PRODUCTS 0F POLYPRO- i 51-0 (I 1 (II) ,PYLENEIMINE/ ,1 '55 51-0 3 (III) Do. i 5lO4 10,000 5 (I) 18 (III) 2 (II) Do. 52-0.- 10,000 Octylene oxide, 4 mols Do. Mol. Mols of alkylene oxide p er j 530 10, 000 Epoxide 201 (Carbide and D0. Weight of mol of polypropyleneimine Physical Carbon), 1 mol Ex. polyproproperties 5 O1 pylene- Eto P O 0 54-0 i r u r imne MP0!" 500 1 I Viscgus liquid. 55-01..

Do: ;6 55-05.. -Viscous Liquid.

TABLE IIA-Continued M01. Mols of alkyleue oxide per weight of 11101 of polypropyleneimine Physical Ex. polyproproperties pylene imine EtO PrO B110 59-02.. D0. 59-03.. DO. 59O4 D0. 59O5 D0. 60-O1.. D0. 60-01 D0. 60-03 Do. 60-04 DO. 61-01 D0. 61-01 D0. 61-03 DO. 61-04 D0. 62-01 D0. 62-02 D0.

ACYLATION THEN OXYALKYLATION Prior acylated polyethyleneimine can be oxyalkylated in the above manner by starting with aeylated polyethyleneimine instead of the unreacted polymer. Non-limiting examples are presented in the following tables. The symbol employed to designate an acylated, oxyalkylated polyethyleneimine is A0. Specifically 1-A O represents acylated, then oxyalkylated polyethlyeneimine.

Example 1A O For this example an autoclave equipped to handle alkylene oxides is necessary. 1671 grams (1 mole) of 1A are charged into the autoclave. Following a nitrogen purge and the addition of 75 grams of sodium methylate, the temperature is raised to 135 C. and 2436 grams of PrO (42 mols) are added. At the completion of this reaction, 440 grams of EtO mols) are added and the reaction allowed to go to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent. Ratio of reactants 1 mole starting material/Pro 42 mols/EtO 10 mols.

Example 2A O For this example a conventional autoclave equipped to handle alkylene oxides is necessary". 525 grams of 2A (0.1 mol) are charged into the autoclave. The charge is catalyzed with grams of sodium methylate, purged with nitrogen and heated to 150 C. 24.6 grams (0.2 mole) of styrene oxide are added and reacted for four hours with agitation. The resulting product is a dark extremely viscous fluid. Ratio of reactants 1 mole starting material/ 2 moles EtO.

These reactions and other reactions are summarized in the following table.

TABLE III.-OXYALKYLATED, PRIOR ACYLATED POLY- ETHYLENEIMINE [Mols of oxide per mol of reactant] Example EtO PrO BuO Physical properties 14.50 5 Viscous Liquid. 1-A5O 22 Do.

10(11) 42(1) Do. Do. I) Do. Do. Dark, viscous liquid. Solid. Thick liquid.

Do. 10AiOi---- 35 Solid. 10A1O;. 10 Viscous liquid. 11-Az0 5 Do.

11AiO, 8(III) 60(11) 2(1) Do. 12A2O1... 12 Solid.

TABLE IIIA.OXYALKYLATED, PRIOR ACYLATED POLYPROPYLENEIMINE Example EtO PrO BuO Physical properties 15-11101 10 Viscous liquid. 15-A10n D0- 15-A1O3 2(1) 2(II) Do.

15-11204 6(II) 10 (III) 2 1 D0.

15-Az05 4 D0.

16-A1O Epoxide 201 (Carbide and Do.

Carbon), 1 mol 17-As01 10(II) (1) Do.

17-A30z 20 D0- 18-Aa0r 3 Pastg solid.

18-A302 Octylene 5 mols o.

18-Aa03 20(11) 5(1) D0.

Iii-A301 Styrene oxide, 3 mols Do.

19-11302 5(III) 40(11) 2(1) D0.

ill-A303 12(II) 65(I) D0.

20-Ai0i Epiehlorohydrin, 2 mols Do.

20A O3 3 Do.

OXYALKYLATION THEN ACYLATION The prior oxyalkylated polyethyleneimine can be acylated with any of the acylation agents herein disclosed (in contrast to acylation prior to oxyalkylation). Since these reactants also have hydroxy groups, acylation, in addition to reaction with amino groups noted above, also includes esterification.

The method of acylation in this instance is similar to that carried out with polyethyleneimine itself, i.e., dehydration wherein the removal of water is a test of the completion of the reaction.

Example 1-O A One mole of 1-0 (1120 grams) in 500 ml. of xylene is mixed with three moles of acetic acid (180 grams) at room temperature. The temperature is raised slowly to -130 C. and refluxed gently for one hour. The temperature is then raised to ISO-160 C. and heated until 3 moles of water and all of the xylene are stripped oil. The dark product is water-soluble.

Example 2-O A 0.1 mole of 2-0 (380 grams) in 400 ml. of xylene is mixed with 0.1 mole of palmitic acid (25.6 grams) at room temperature. Ratio 1 mole 2-0 to 1 mole of palmitic acid. Vacuum is applied and the temperature is raised slowly until one mole of water (18 grams) is removed. This product is a dark viscous liquid.

Example 2-O A 0.1 mole of 2-0 (757 grams) is mixed with 500 grams of xylene and heated to 100 C. 0.1 mole of diglycolic acid (134 grams) is added slowly to prevent excessive 'foaming. Ratio 1 mole 2-0 to 1 mole glycolic acid. The temperature is raised to -150 C. and held until one mole of water has evolved. This product is the diglycolic acid fractional ester of 2-0 A white precipitate forms during this reaction which can be removed by filtration. Analysis shows the precipitate to be sodium acid diglycolate, a reaction product of the catalyst and diglycolic acid. The filtered product is a dark viscous liquid at room temperature.

Table IV contains examples which further illustrate the invention. The symbol employed to designate oxyalkylated, acylated products is 0A.

TABLE IV.ACYLATED, PRIOR OXYALKYLATED POLY- ETHYLENEIMINE Mols of Ratio mols aeylating of Water Example Aeylating agent per removed to Physical agent mol oxymols aeylatproperties alkylated ing agent PE employed Acetic 3 1 Dark viscous quid. Laurle 1 1 Do. Acetic 2 1 Solid.

' 3 1 Do. 1 1 Do. 1 1. Do. 2 1 Do. 1 Viscous liquid. 2 1 Do. 1 1 Do. 2 1 Do. 1 1 Do. 1 1 D0. 1 2 Do. 2 1 Do. 1 1 Do. 1 Do.

Linoleic 3 1 Do. Palmitie 1 1 Do. Acetic 1 1 Do. 25O:A1 Dimerie 1 1 Solid.

(Emery Indus.) 25-O3A2. Dxglyeol1e 1 1 Do. 26O1A D1phenol1c 1 1 Do. 26O A Terephthalie 1 1 Do. 26-0511..-" Benzoie 1 1 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IVA.ACYLATED, PRIOR OXhgALKYLATED POLY- PROPYLENEIMIN Mols of aeyl- Ratio mols ating agent of water Example Acylating per mol of removed to Physical agent oxyalkylated mols of aeylproperties polypropylating agent eneimine employed Oleie 2 2 Thick dark liquid. Diphenolicuh 1 1 Pasty sohd. Laurie 3 1 Do. Acetic 4 1 Do. Naphthenie 1 1 Do. Stearic 2 2 Do. Tall oil 1 1 Do. Maleie 1 D0.

anhydride. Palmitic 2 2 Do. Dimeric 3 1 Waxy solid (Emery Industries) Dig1yc0lie 1 1 Pasty solid Myristie. 2 1 Do. Ricinoleic 1 1 Do. Abietic 2 2 Do. 1 1 Do. 1 1 Do. 1 1 Waxy solid 1 1 Do.

HEAT TREATMENT OF OXYALKYLATED PRODUCTS The oxyalkylated products described herein, for example, those shown in Table II relating to oxyalkylated polyethyleneimine and those in Table III relating to oxyalkylated, prior acyl-ated, polyethyleneimine can be heat treated to form useful compositions.

In general, the heat treatment is carried'out at 200- 250 C. Under dehydrating conditions, where reduced 18 pressure and a fast flow of nitrogen is used, lower temperatures can be employed, for example ISO-200 C.

Water is removed during the reaction, such as by means of a side trap. Nitrogen passing through the reaction mixture and/or reduced pressure can be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chemical formulas for the reason that the structures are subject to a Wide variation.

The heat treatment is believed to result in the polymerization of these compounds and is elfected by heating same at elevated temperatures, generally in the neighborhood of ZOO-270 C., preferably in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats, calcium chloride, iron and the like. The proportion of catalyst employed may vary from slightly less than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of Water formed during the process. At times the process can be conducted most readily by permitting part of the volatile constituents to distill, and subsequently subjecting the vapors to condensation. The condensed volatile distillate usually contains water formed by reaction. The water can be separated from such condensed distillate by any suitable means, for instance, distilling with xylene, so as to carry over the water, and subsequently removing the xylene. The dried condensate is then returned to the reaction chamber for further use. In some instances, condensation can best be conducted in the presence of a high-boiling solvent, which is permitted to distill in such a manner as to remove the water of reaction. In any event, the speed of reaction and the character of the polymerized product depend not only upon the original reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, the time of reaction, and the speed of water removal, i.e., the effectiveness with which the Water of reaction is removed from the combining mass. Polymerization can be efiYected without the use of catalysts in some instances, but such procedure is generally undesirable, due to the fact that the reaction takes a prolonged period of time, and usually a significantly higher temperature. The use of catalyst such as iron, etc. fosters the reaction.

The following examples are presented to illustrate heat treatment. The symbol used to designate a heat treated oxyalkylated polyethyleneimine is OH and an acylated, oxyalkylated product is AOH. In all examples 500 grams of starting material are employed.

Example 2-O H A conventional glass resin vessel equipped with a stirrer and water trap is used. Five hundred grams of 2*O are charged into the above resin vessel along with five grams of CaCI The temperature is raised to 225250 C. and heated until 57 grams of water (3.2 mols) are evolved. This process takes 7.5 hours of heating. The product is an extremely viscous material at room temperature. However, upon warming slightly this product dissolves easily in water.

Example 19O H The process of the immediately previous example is repeated using l9O but substituting sodium methylate for calcium chloride. The product is a dark, viscous, watersoluble material.

Example 15O H The process of Example 2-O H is repeated using 15-0 but substituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (1) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATED POLYETHYLENEIMINE Water Removed Example Reaction Catalyst (5 grams) Time Physical properties Temp, C in hours Grams Mols 74 4.1 8. Dark, viscous liquid. 67 3. 2 16. Do. 36 2.0 23 Do. 38 2.1 30 D0. 95 5.3 9. 5 Solid. 32 1. 8 l2 Viscous liquid. 40 2.2 13 Do. 72 4 18 Do. 64 3 24 D0. 90 5 30 Do; 54 3 16 Do. 36 2 18 Do. 76 4. 2 Solid. 54 3 16 Viscous liquid. 63 3. 5 8 Do. 57 3. 2 12 Do. 36 2 14 Do. 38 2.1 11 D0. 40 2. 2 13 D0: 36 2.0 16 Paste. 40 2.2 8 Do. 11-A:;O1H. 90 5 14 D0. 12-A20 2H.-. 32 1. 8 18 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE VA.-HEAT TREATED (1) OXYALKYLATED AND (2) ACYLAIED, OXYALKYLATED POLYPROPYLENEIMINE Water Removed Example Reaction Catalyst (5 grams) Time Physical properties Temp., C. in hours Grams Mols 32 1. 8 18 Dark, viscous liquid.

54 3. 0 24 Pasty.

40 2. 2 i3 Viscous liquid.

57 3. 2 12 Paste. 17-HaO2H... 54 3.0 16 Do. 19-A3O1H... 36 2.0 18 Do. 20A1O1H 90 5.0 30 Do. 20 A1OsH 32 1. 8 12 D0.

ALKYLATIO-N Alkylation relates to the reaction of polyethyleneimine and derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g. alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; Z-ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7- ethyl-Z-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyi fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen as, for example, where dichloroethyl ether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of mono-Chlorowax have been set forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and polyethyleneimine is a condensation reaction, or an alkylation reaction, characterized by the elimination of hydrogen halide, the general conditions for such reactions are applicable herein. For certain uses it is preferable to carry out the reaction at temperatures of between about and about 250 0., preferably between about C. and about 200 C., in the presence of a basic material which is capable of reacting with the hydrogen halide to remove it. Such basic materials are, for example, sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl amines, alkali or alkaline earth metal hydroxides, and the like.

It is preferred to perform the reaction between the alkyl halide reactant and polyethylenei'mine in a hydrocarbon solvent under reflux conditions. The aromatic hy- 21 drocarbon solvents of the benzene series are especially preferable. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction Vessel and on the reaction temperature selected. For example, it will be apparent that the amount of solvent used can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the hydrogen halide from the reaction mixture. In practice, the reaction is continued until no more hydrogen halide is for-med. In general, the time of reaction will vary widely, such as between about four and about ten hours.

It can be postulated that the reaction between the alkyl halide reactant and polyethyleneimine results in the formation of products where the alkyl group of the alkyl halide has replaced a hydrogen atom attached to a nitro gen atom. It is also conceivable that alkylation of an alkylene group of polyethyleneimine can occur. However, the exact composition of any given reaction product cannot be predicted. For example, when two moles of butyl bromide are reacted with one mole of polyethyleneimine 900, a mixture of mono-, diand triand higher N-alkylated products can be produced. Likewise, the alkyl groups can be substituted on different nitrogen atoms in different molecules of polyethyleneimine.

Thus, the term alkylation as employed herein and in the claims include alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkyl halide with the polyethyleneimine at the desired ratio in the presence of one equivalent of base for each equivalent HCl given off during the reaction. Water formed during the reaction is removed by distillation. Where the presence of the anions, such as chlorine, bromine, etc., is not material and salts and quaternary compounds are desired, no base is added.

The following examples are presented to illustrate al kylation of polyethyleneimine.

In these examples, the term mesomer is employed. A mesomer is defined as a repeating radical which, when combined with other mesomers, forms the principal portion of the polymer molecule.

Thus, the unit is the mesomer of polyethyleneimine, since polyethyleneimine' may be represented by the formula Example -K 430 grams of polyethyleneimine 50,000, equivalent to mesomeric units of ethyleneimine, in 500 ml. of xylene and 570 grams of sodium carbonate, equivalent to 8 moles, are placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser take-off for removal of volatile components. The stirred reactants are heated to about 100 C. whereupon 1140 g. (8 mols) of dichloroethyl ether is started in slowly at such a rate that the temperature of the reaction vessel contents never exceeds 165 C., but preferably stays around 135 C. The reaction is exothermic and 5-6 hours are required to add all the dichloroethyl ether. After all the dichloroethyl ether has been added, the temperature is allowed to drop to about 90100 whereupon reduced pressure is applied to the reaction vessel and all xylene stripped out. The material left in the vessel is a thick brown liquid which solidifies upon cooling to a glassy-solid.

Example 8-A The equivalent of 8 mesomeric units, based on polyethyleneimine, of the material 8-A (Table I) in 300 g. xylene is placed in a reaction vessel described in the above example for 5-K 340 grams anhydrous sodium carbonate, equivalent to 3.2 moles are added followed by 1.6 moles dimethyl sulfate. The temperature is then brought up to 125 C. and held there for a period of 6-8 hours. Xylene is then removed under reduced temperature and pressure conditions as in the example for 5K The resulting product, a dark amber material, is very viscous at ordinary temperature.

Example 20O H K The equivalent of 10 mesomeric units based on polyethyleneimine of the material 20-O H (Table V) in 300 ml. of xylene and 420 grams sodium bicarbonate, equivalent to 5 moles, are placed in an autoclave equipped with a stirring device, a thermometer and a condenser reflux device which can be closed off from the autoclave during reactions in which pressures above atmosphere are experienced. The autoclave is closed and heat is applied to bring up the temperature to 120-130" C. at which time 5 mols methyl chloride are added slowly while never allowing pressure to exceed 5 atmospheres pressure. Several hours will be necessary to get all methyl chloride in and pressure inside the vessel down to one atmosphere. At this point the reflux condenser is opened, the temperature is allowed to drop to 100 C. and a slight vacuum applied in order to reflux the xylene out of the autoclave. The resulting material is a very viscous amber colored liquid.

The reactions shown in the following table are carried out in a similar manner. Each reaction in the table is carried out in two ways(1) in the presence of base, as in 5K to yield the alkylation product and (2) in the absence of base to yield the halogen-containing or sulfate-containing (5-K X) products.

The alkylated products of this invention contain primary, secondary, tertiary, and quaternary amino groups. By controlling the amount of .alkylation agent employed and the conditions of the reaction, etc., one can control the type and amount of alkylation. For example, by reaction less than the stoichiometric amount of alkylation agent one could preserve the presence of nitrogen-bonded hydrogen present on the molecule and by exhaustive alkylation in the presence of sufiicient basic material, one can form more highly alkylated compounds.

The moles of alkylating agent reacted with polyethyleneimine will depend on the number of alkylation reactive positions contained therein as well as the number of moles of alkylating agent one wishes to incorporate into the molecule. Theoretically, every hydrogen bonded to a nitrogen atom can be alkylated. We have advantageously reacted l-20 moles of alkylating agent per moles of polyethyleneimine 900 but preferably l-l2 moles. With polyethyleneimine 20,000 greater amounts of alkylating agent can be employed, for example 1-50 moles, and with polyethyleneimine 40,000, 1*100 moles, etc. Optimum alkylation will depend on the particular application.

.In addition, the alkyl halide may contain functional groups. For example, chloroacetic acid can be reacted with polyethyleneimine to carboxylic acid groups.

-PNCH COOH, wherein P is the residue of polyethylenelmme.

In addition, polyethyleneimine can be alkylated with an alkyl halide such as alkyl chloride and then reacted with chloroacetic acid to yield an alkylated polyethyleneimine containing carboxylic acid groups yield a compound containing 23 The symbol employed to designate an alkylated polyethyleneimine is K. Where the product is a salt or a quarternary the symbol is KX. Thus, for example, where no acceptor base is employed and a salt is allowed to form lA O K would be 1A O KX.

TABLE VI.ALKYLATED PRODUCTS Mols M01. alkylating Physical Example wt. Alkylating agent agent per properties PE mesomer unit Allyl chloride 0. 2 Viscous liquid. .-...do 0.7 Do. nzyl chloride. 0.3 o. -do 0. 8 Solid.

Methyl chloride. 0. 3 Viscous liquid. .-...do 1.0 Solid.

Ethylene dichloride. 0.2 Viscous liquid .-...do 0.5 Do. 1,4-dichlorobutene-2. 0. 2 Do. 0.5 Do. 0.2 Do. 0. 4 Do. Dodecylbenzene 0. 2 Solid.

chloride. .do 0.5 Do. Butyl chloride 0.3 Viscous liquid ..--.do 0.6 Do. Dichlorodiethyl 0. 2 Do.

ether. ..do 0.8 Solid.

Benzyl chloride 0. 3 Viscous liquid 0 do 0.8 Solid.

Ethylene dichloride. 0. 2 Viscous liquid. .-...do 0.8 Do. Methyl chloride. 0. 3 Do. do 1.0 Solid.

l,4 xylidene 0. 2 Viscous chloride. liquid. ..do 0.2 Do.

- Dodecenyl chloride.. 0.2 Solid.

Methyl chloride. 0. 5 Viscous liquid. Benzyl chloride. 0. 4 Solid. Dimethyl sulfate.-. 0.2 Viscous liquid. Dichlorodiethyl 0. 4 D0.

ether. 1,4-dichlorobutene-2. 0. 3 Do. Benzyl chloride. 0. 4 Solid. Methyl chloride.. 0.7 Do. Ethylene dichloride. 0.2 Viscous liquid. Benzyl chloride. 0. 4 Solid. Dimethyl sulfate.-. 0.2 Viscous liquid. Dichlorodiethyl 0. 4 Solid.

ether. Methyl chloride. 0. 6 D0. Dodecyl benzyl 0.2 Do.

chloride. 1,4-xylylene 0.2 Viscous dichloride. liquid. Benzyl chloride. O. 5 Solid. Methyl chloride. 0. 6 Do. Dodecenyl chloride-. 0. 2 Do. Ethylene dichloride. 0 3 Viscous liquid. 1,4-dichlorobutene-2. 0.2 Do.

Benzyl chloride. 0. 4 Solid Dichlorodiethyl 0. 4 Do.

ether. Methyl chloride.--.. 0.5 Do. Octadecyl chloride. 0. 2 Do. Benzyl chloride. 0. 4 Do. 14-O AK. Dichlorodiethyl 0. 3 Viscous ether. liquid. 22-O AK- Methyl chloride..--. 0. 6 Do. 26-O5AK. Benzyl chloride 0.6 Solid. 1-OzHK ..do 0.4 Do. 7-OHK Dichlorodiethyl 0.2 Viscous ether. liquid 11-0 rHK. Ethylene dichloride. O. 2 Do. -OrHK. Methyl chloride.-.-. 0.5 Do. -OzHK Dimethyl sulfate. 0.2 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE VI-A.-AOYLATED PRODUCTS Mols of Moi. wt. alkylating Physical Example of PE Alkylating agent agent per properties mesomer unit Allyl chloride 0.2 Viscous liquid --do 0. 7 Do. Benzyl chloride. 0.3 Do. o 0.8 Do. ethyl chloride. 0.7 Do. ..do 1. 0 Do. ylene dichloride. 0.2 Do. do 0. 5 Do. chlorobutene-2. 0. 2 D0. 0.5 Do. 0.2 Do. o 0. 4 Do.

Dodecylbenzene 0. 2 Solid.

chloride.

0.5 Do. 0.3 Do. 0. 6 Do. 0.2 Do.

0.8 Do. 0.3 Do. .-...do 0.8 Do. 0 Methyl chloride. 0.3 Do. --..-do 0.8 Do. Allyl chloride. 0. 5 Do. Dimethyl sulfate. 0. 8 Viscous liquid. Methyl chloride. 0. 3 Do. Ethylene dichloride. 0. 8 Do. Dichlorodiethyl 0. 2 Solid.

ether. Benzyl chloride. 0.6 Do. 1,4-dichlorobutene-2 0. 3 Do. Dodecenyl chloride. 0.5 Viscous liquid. Benzyl chloride...-- 0.2 Do. 1,4-xylylene dichlo- 1.0 Do.

ride. Dedecyl benzene 0.8 Do.

chloride. Dimethyl sulfate.-. 0. 3 Solid. Ethylene dichloride. 0.7 o. Butyl chloride 0.2 Do. Allyl chloride. 0.5 Do. Benzyl chlorid 0.3 Viscous liquid 15-A2O4K.... Methyl chloride.. 1.0 Solid. 19-A3O1K.-. Ethylene dichloride. 0. 6 Do. 19-A3O3K.... Dichloro pentane.... 0.5 Do. 27OzAK-- Dichlorodiethyl 0. 2 Do.

ether. Dimethyl sulfate. 1. 0 Do. Methyl chloride 0.8 Do. Allyl chloride. 0. 5 Do Butyl chloride 0.2 Do.

In addition to the above examples wherein a base acceptor is employed to remove the acid anion such as halogen, sulfate, etc., the above examples are also prepared omitting the inorganic base from the reaction medium. When this is done, a halogen containing salt, quaternary, etc. is formed. Examples where such salts are formed will be designated as above except that they will contain an X designation for example instead of l-O A K they will be 1-O A KX, and instead of 22O =,AK they will be 22-O AKX, etc. X indicates salt formation.

ALKYLATED, THEN ACYLATION The alkylated material prepared above can be further treated with acylating agent where residual acylatable amino groups are still present on the molecule. The acylation procedure is essentially that described above wherein carboxylic acids react with the alkylated polyethyleneimine under dehydrating conditions to form amides and cyclic amidines. The product depends on the ratio of moles of water removed for each carboxylic acid group, i.e., 1

TABLE VII.-ACYLATED, PRIOR ALKYLATED POLYETH YLENEIMINE OR DERIVATIVE Ratio mols Mols of acylating water re- Examplc Acylating agent per moved per Physical Agent mol polyethmole of properties yleneimine reactant deriv.

l-KzA Lauric 4:1 1 Viscous liqgid. Oleic 1 :1 1. 0. 1:1 1 Do. 0. 5:1 1 Solid.

2:1 1 Viscous liquid. 5K A. Rieinoleic 2:1 1 8 Do. 5-K A Succinic an- 2:1 1 Do.

hydride alkyl (C12). 5-K4A Stearie 1:1 1. 5 Solid. 6-K A.. Myristic. 2:1 1 Viscous liquid 2-A4KA Aeetic 2:1 1 Do. 6A4KA Diglyco 1:1 1 Do. 2-O1KA Lauric 2:1 1 Viscous liquid. 1-O2KA Oleic 2:1 1.3 Do. 102HKA Maleic an- 1:1 Solid.

hydride.

The following table presents specific illustrations of compounds other than polyethyleneimine and its derivatives.

TABLE VIIA.ACYLATED, PRIOR ALKYLATED POLY- PROPYLENEIMINE OR DERIVATIVE Ratio mols oi acylating Mols of water Example Acylating agent per mol removed per Physical Agent of polypromol of properties pyleneimine reactant deriv.

7K A.. Myristic 2:1 1 Viscous liquid. Acetic 2:1 1 Do. Diglycolic 1 :1 1 Do. Lauric 2:1 1 Do. Oleic 2:1 1. 3 Do. 12K1A Maleic 1:1 Solid.

anhydride. 16-A3KA Laurie 4:1 1 Viscous liquid 20A KA Oleic 1:1 1.5 Do. 28O2KA Palmitic 1:1 1 Do. 44-O5KA imeric 0. 5:1 1 Do. 61-O2KA Nonanoic- 2: 1 1 Do. AzO4KA Ricinoleic 2:1 1.8 Do. 19AaO KA. Alkyl 2:1 Solid.

succinic anhydride 1a)- 44O AKA Stearic 1:1 1 Viscous 1i uid 46-O;HKA. Myristic 2:1 1 o. 20AiOzHKA Acetic 1:1 1 Do.

OLEFINATION of polyethyleneimine Where the compound contains an additional active hydrogen, other unsaturated molecules can be added to the original molecule for example:

Where one or more active hydrogens are present at another reactive site, the following reaction could take place:

The reaction is carried out in the conventional manner such as illustrated, for example, in Synthetic Organic Chemistry, Wagner & Zook (Wiley, 1953), page 673.

Non-limiting examples of unsaturated compounds which can be reacted with the polyamine and derivatives thereof including the following-acrylonitrile, acrylic and methacrylic acids and esters, crotonic acid and esters, cinnamic acid and esters, styrene, styrene derivatives and related compounds, butadiene, vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, etc.

In addition, polyethyleneimine and derivatives thereof containing active hydrogens can be used to prepare telomers of polymer prepared from vinyl monomers.

The following are examples of olefination. The symbol employed to designate olefination is U and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glass resin apparatus. Since the reaction is that of a double bond with an active hydrogen, no water is eliminated. The reaction is relatively simple, as shown by the following example:

Charge 900 grams of polyethyleneimine 900 in xylene (1 mol) into glass resin apparatus. Care should be taken that the PEI 900 is water-free, to eliminate undesirable side reactions. At room temperature, slowly add 53 grams of acrylonitrile (1 mol). The reaction proceeds smoothly without the aid of a catalyst. Warm gently to 100 C. and stir for one hour.

Example 6U To 1,000 grams of polyethyleneimine 100,000 (0.1 mol) in 300 grams of xylene, add 1.24 grams of divinyl sulfone (0.01 mol) at room temperature. This reaction is exothermic and the ambient temperature is employed.

Example 2O KAU Same reactions as Example 1-U except that 1 mol of methyl acrylate is substituted for acrylonitrile and 2O KA is substituted for the polyethyleneimine 900. Part of this product is thereupon saponified with sodium hydroxide to form the fatty amino acid salt.

Further examples of the reaction are summarized in the following table:

TAB LE VIII.O LE FINATION M01. weight Mols of Temp., Example 0t polyethyl- Olefin olefin per Time C;

eneirnine mol PE 900 Aerylonitrlle 1:1 900 Methylacrylate. 2:1 Sty 3:1 2:1 2:1 2:1 1:1 1:1 2:1 1:1 1:1 3:1 3:1 Acrylonitrile 3:1 3:1 1:1 2:1 100,000 Dioctyl maleate 2:1

Mols oi Olefin olefin per Mol PE Styrene 1:1 Divinyl sulfone 1:1 Methylaerylate 1 :1 Divinyl sullone 1:1 3:1 1 :1 2:1 2:1 1:1 4: 1 3: 1 3:1 3: 1 1:1 1:1 2:1 1:1 2:1 2: 1 2:1 Styrene 3:1 Methylaery1ate.-- 2:1 1-O2HKAU-- Acrylonitrile 1 1 The following table presents specific illustration of compounds other than polyethyleneimine tives.

TABLE VIIIA.O LE FINATION and its deriva- 45 OF POLYPROPYLENEIMINE CARBONYLATION Carbonylation relates to the reaction of polyethyleneimine and derivatives thereof with aldehydes and ketones.

Where primary amino groups are present on the polyethyleneimine reactants, SchifPs bases can be formed on reaction with carbonyl compounds. For example, Where an aldehyde such as salicylaldehyde is reacted with polyethyleneirnine 900 in a ratio of 2 moles of aldehyde to 1 mole of PE 900, the following type of compound could be formed:

r C=N- CHnCHnN mCHaCHzN=C etc., and other isomeric configurations, such as Where the Schifls base is present on the non-terminal amino group rather than on the terminal amino group, etc.

A wide variety of aldehyde may be employed such as aliphatic, aromatic, cycloaliphatic, heterocyclic, etc., including substituted derivatives such as those containing 30 4-hydroxyquinoline-aldehyde-3 7-hydroxyquinoline-aldehyde-8 Formaldehyde Glyoxal Glyceraldehyde Schiffs bases are prepared with the polyethyleneimines of this invention in a conventional manner such as described in Synthetic Organic Chemistry, by Wagner & Zook (1953, Wiley), pages 728-9.

Where more extreme conditions are employed, the products may be more complex wherein the carbonyl reactant instead of reacting intramolecularly in the case of a Schifl?s base may react intermolecularly so as to act as a bridging means between two or more polyethylenearyloxy, halogen, heterocyclic, amino, nitro, cyano, m ne compounds, thus increasing the molecular weight carboxyl, etc. groups thereof. Non-limiting example are of the polyethyleneimrne as schematlcally shown below 1n the f ll i the case where formaldehyde is the carbonyl compound: Aldehydes: P (CH2 P)11*CH2 Benzaldehyde 2 In addition to increasing the molecular weight by means g methylbenzaldehyde of aldehydes, these compounds result in the formation of 3 methylbenzaqdehyde cyclic compounds. Probably both molecular weight in- 4 methylbenzaldehyde crease and cyclization occur during the reaction. z methoxybenzaldehyde The following examples illustrate the reaction of car- 4 methoxybenzaldehyde bonyl compounds with polyethyleneimines. The symbol wNaphthaldehyde employed to designate carbonylation is C, acylation, 5 Naphtha1dehyde carbonylation AC, and alkylation, carbonylation KC. 4-phenylbenzaldehyde Example 1-C Efgggififijggg: Charge 900 grams of polyethyleneimine 900 and 900 Heptaldehyde grams of Xylene into a conventional glass resin apparatus Aldol fitted with a stirrer, thermometer and side-arm trap. Raise temperature to 90 C. and slowly add 44 grams of acetalgiggigigi ggziggi ggf dehyde (1 mol). Hold at this temperature for three 2 hydroXy 3 mgthoxybenzaldehyde hours. Vacuum is then applied until all xylene is stripped 2 4 dihydroxybgnzaldehyde 011. The reaction mass is a thick dark liquid which 1s 2-6-dihydroxybenzaldehyde Soluble 111 Water E l 5 c Z-hydroxynaphthaldehyde-1 xam'p e 1 1-hydroXynaphthaldehyde-2 Using the same apparatus as above, charge 500 g. (0.1) Anthrol-Z-aldehyde-l 40 of polyethyleneimine 5,000. While stirring, add slowly at Z-hydroxyfiuorene-aldehyde-1 room temperature 8.2 grams of 37% aqueous formalde 4-hydroxydiphenyl-aldehyde-3 hyde (0.1 mol of HCHO). After the reaction has ceased, 3-hydroxyphenanthrene-aldehyde-4 raise temperature to 100 C. The reaction mass may be 1=3-dihydroXy-2-4-dialdehydebenzene sto ped at this point. It is a viscous water-soluble matep Z-hydroxy-S-chlorobenzaldehyde r-l-al. However, 1t 1s possrble to continue heating under 2-hydroxy-3 :S-dibromobenzaldehyde vacuum until all of the water has been eliminated. Cross- 2-hydroxy-3-nitrobenzaldehyde linking occurs with this procedure and care must be taken 2-hydroxy-3-cyanobenzaldehyde to prevent insolubilization. 2-hydroxy-3-carboxybenzaldehyde Further examples of this reaction are summarized in 4-hydroxypyndine-aldehyde-3 the following table: 7

TABLE IX.CARBONYLATION M01 ratio M01 weight of aldehyde to Example polyethyl- Aldehyde polyethyl- Temp., C Time 611811111119 611011111119 or deriv.

900 Acetaldehyde-- 1:1 3hours 900 do 2:1 90 D0. 900 .do 3:1 90 D0. 5,000 Heptaldehyde 5:1 4 hours 5,000 do 3:1 125 Do 1:1 125 Do 2:1 80 lhour. 1:1 80 Do. 11,500 d0 0.511 80 Do. 20,000 salicylaldehydmu 6:1 3hours 20,000 d 5:1 140 Do 3:1 140 Do. 3:1 (1) 1 hour. 2:1 (1) Do. 2-.1 (l) Do. 7 6:1 125 5hou1s 311 125 0 2:1 125 Do 3:1 120 2hours 2:1 120 Do 100,00 d0 111 120 Do. 100,000 Benzaldehyde 3:1 110 1 hour. 100,000 do 21 110 D0 TABLE IX.Continued Moi ratio Example Aldehyde aldehyde to Temp., C. Time polyethylenelmine 1:1 110 1 hour. 3:1 100 2 hours. 2:1 100 Do. 1:1 100 Do. 3:1 (2) 1 hour. 2:1 (2) Do. 1:1 (2) Do. 3:1 130 4 hours. 2:1 130 0. 3:1 100 1 hour. 2:1 100 Do. 1:1 100 D0. 3:1 140 6 hours. 2:1 140 Do. 1:1 140 Do. 3:1 (2) 1 hour. 2:1 (2) Do. 1:1 (2) Do.

1 Start at 25 C., raise to 100 C.

2 Start at 25 0., raise to 90 C The following table presents speclfic mllustration of compounds other than polyethylenelmme and 1ts derivatlvcs.

TABLE IXA.CARBONYLAT1ON Molecular M01 ratio Example weight of Aldehyde aldehyde to Temp., Time in polypropylpolypropyl- 0. hours eneimine eneimlne 500 Benzaldehyde 1:1 110 lhour. 500 do 2:1 110 Do. 500 do 3:1 110 Do. 1,000 Salicylaldehyde... 4:1 120 Do. 1,000 do 31 120 Do. 1,000 -do 2:1 120 Do. 5,000 Formaldehyde- 2:1 90 Do. 5,000 -do 1:1 90 D0. 0.5:1 90 Do. 2:1 90 Do. 1:1 90 Do. 0.5:1 90 D0. 3:1 100 2 hours 2:1 100 Do. 1:1 100 Do. 4:1 130 3 hours. 3:1 130 D0.

M01 ratio of aldehyde to Time in Example Aldehyde polypropyl- Temp., Hours 811811111118 01' derivative -1130 Glyceraldehyde 3:1 125 4 18-A3G.-. Heptaldehyde.-. 2:1 125 4 Furluraldehyde. 1:1 100 2 1:1 90 1 4:1 120 2 1:1 (1) 1 1:1 100 2 2:1 100 2 3:1 100 2 1:1 130 3 2:1 130 3 3:1 130 3 3:1 125 2 2:1 125 2 1:1 125 2 2:1 100 1 1:1 100 1 05:1 100 1 2:1 70 1 1:1 70 1 1 Start at 0., raise to 100 C.

The examples presented above are non-hnntmg ex- Example des1gnat10n: Meaning amples. It should be clearly understood that various other A Acylated. combinations, order of reactions, reactlon ratlos, mult1- A0 Acylated, then oxyalkylatedplic-ity of add1t1ons, etc., can be employed. Where addi- (3) AOA Acylated, then oxyalkylated, tional reactive groups are still present on the molecule, then acrylatedthe react1on can be repeated w1th either the original reac- (4) AOH illl g, en Oxyalkylated, tant or another reactant. en eat treated (5) AX Salt or quaternary of (1).

The type of compound prepared 1s evident from the let- (6) AOX Salt or quaternary of (2) ters ass gned to the examples. 'lhus, taking the branched (7) AOAX Salt or quaternary of (3), poly-amine as the starting material, the following example (3) A-QHX Salt or quaternary f (4),

designations have the following meaning:

(9) O Oxyalkylated.

Example designation: Meaning 0A Oxyalkylated, then acylated. (11) OH Oxyalkylated, then heat treated. (12) K Alkylated. (13) KX Salt or quaternary of (12). (14) KA Alkylated, then acylated. (15) AK 1 Acylated, then alkylated. (16) AKX Salt or quaternary of (15). (17) OK Oxyalkylated, then alkylated. (18) OKX Salt or quaternary of (17). (19) C Carbonylated. (20) AC Acylated, then carbonylated. (21) KC Alkylated, then carbonylated. (22) CO Carbonylated, then oxyalkylated.

(23) U Olefinated. (24) AU Acylated, then olefinated. (25) KU Alkylated, then olefinated. (26-) KUX Salt or quaternary of (25).

In addition to polyethyleneimine itself, other polyalkyleneimines can be employed, a typical example of which is polypropyleneimines. Propyleneimine is now commercially available and can be polymerized to the polymer and polypropyleneimine can then be reacted in a manner similar to those reactions shown above. Thus, the teachings contained herein also apply to other polyalkyleneimines besides polyethyleneimine and derivatives thereof.

USE AS A CHELATING AGENT 'in which respect they resemble the aromatic rings of organic chemistry. Because of the great afiinity of chelating compounds for metals and because of the great stability of the chelates they form, they are very important industrially.

The compositions of this invention are excellent chelating agents. They are particularly suitable for forming chelates of great stability with a wide variety of metals.

Chelating metals comprise magnesium, aluminum, arsenic, antimony, chromium, iron, cobalt, nickel, palladium, and platinum. Particularly preferred of such metals as chelate constituents are iron, nickel, copper and cobalt.

The chelates formed from the compositions of our invention are useful as bactericidal and fungicidal agents, particularly in the case 'of the copper c'helates. In addition the chelates can be employed to stabilize hydrocarbon oils against the deleterious eifects of oxidation.

In general, these chelates are prepared by addin-g'a sufficient amount of a metal salt to combine with a compound of this invention. They are prepared by the general method described in detail by Hunter and Marriott in the Journal of the Chemical Society (London), 1937, 2000, which relates to the formation of chelates from metal ions and salicylidene imines.

The following examples are illustrative of the preparation of chelates.

' Example 1-A An aqueous 0.1 mole solution of the chelating agent of Example 1-A7 is added to an aqueous solution of 0.02 mole cupric acetate. The solution becomes darker in blue color immediately with the formation of the copper chelate. Inability of the solution to plate out copper on a clean and polished iron strip indicates that the copper is effectively removed from solution by the formation of a chelate.

Example 1-0 An aqueous solution of 0.1 mole of the chelating agent of Example 1-0 is added to an aqueous solution containing 0.025 mole ferrous sulfate. Lack of the usual formation of a red-sediment in the water subsequently due to oxidation and precipitation of iron as hydrated oxide shows the ironhad been chelated while in the ferrous form by the reagent l-O and thus effectively removed from further reactions.

Example 1A O An aqueous solution of 0.1 mole of the chelating agent 1-A O is treated with an aqueous solution containing 0.01 mole nickelous-acetate. The solution turns to a darker green indicating that a chelate type of material had been formed.

To avoid repetitive detail, chelates are formed from the above copper, iron and nickel salts and the compounds shown in the following table.

Chelating agents:

Polyethyleneimine, molecular wt. 900 Polyethyleneimine, molecular wt. 5,000 Polyethyleneimine, molecular wt. 11,500 Polyethyleneimine, molecular Wt. 20,000 Polyethyleneimine, molecular Wt. 50,000 Polyethyleneimine, molecular Wt. 100,000

Polypropyleneimine, molecular wt. 500 Polypropyleneimine, molecular 1,000 Polypropyleneimine, molecular wt. 5,000 Polypropyleneimine, molecular wt. 10,000 Polypropyleneimine, molecular wt. 20,000 Polypropyleneimine, molecular wt. 40,000

USE IN EMULSION FLUIDS FOR DRILLING WELLS drilling fluid useful in drilling oil and gas wells.

Fluids commonly used for the drilling of oil and gas 'wells are of two general types: water-base drilling fluids comprising, for example, a clay suspended in water, and oilrbase. drilling fluids comprising, for example, a clay or calcium carbonate suspended in mineral oil.

A third type of drilling fluid, which has recently been developed, is one of oil-in-Water or water-in-oil emulsions, for example, emulsions of mineral oil in water or water in mineral oil formed by means of emulsifiers such as: sulfuric acid; Turkey-red oil; soaps of fatty acids, for example, sodium oleate; emulsoid colloids, for example starch, sodium alginate, etc. Varying amounts of finelydivided clay, silica, calcium carbonate, blown asphalt,

35 and other materials may be added to these emulsions to improve their properties and control their weight.

The use of drilling emulsions has several advantages over the use of either water-base or oil-base drilling fluids.

Drilling emulsions are generally superior to water-base drilling fluids in forming a very thin substantially fluidimpervious medsheath on the walls of a borehole, in eliminating fluid loss to the formation and contamination of producing formations by an aqueous liquid, etc.

Drilling emulsions are generally superior to oil-base drilling fluids from the point of View of cost, of ease of handling, of suitability for electrical logging, etc.

The disadvantage for general use of drilling emulsions is, however, their lack of stability in the presence of even moderately high concentrations of electrolytes such as brines entering the borehole from the formation and becoming admixed to the drilling fluid.

Thus, drilling emulsions, formed by means of the emulsifiers listed above break down immediately or after a few hours of use or storage upon contamination with small concentrations of electrolytes, such as, for example, a 1% solution of sodium chloride. However, the present compounds provide an improved oil and water drilling emulsion or fluid which is substantially stable in the presence of contaminating formation salts or brines.

This phase of the present invention relates to drilling fluids of improved characteristics prepared by forming emulsions comprising oil, water, the compounds of this invention and, if desired various amounts of finely-divided clay, silica, calcium carbonate, and other materials to control the properties or weight of the drilling fluid.

Of the two general types of oil and water emulsion, i.e., oil-in-water and water-in-oil emulsions, the present invention is primarily concerned with oil-in-water emulsions where the oil is present in the dispersed phase while the water forms the continuous phase.

Various methods may be selectively used in forming well drilling emulsions by means of the agents of the present invention.

If it is desired to prepare a very light or low specific gravity drilling emulsion, a mineral oil, such as crude oil, gas oil, diesel oil, etc., is emulsified directly in water by means of a high speed hopper or a jet device, such as a so-called mud-gun, in the presence of a relatively small quantity, such as from 0.5 to by weight or higher but preferably 2 to 3% by weight, based on the weight of oil plus water, of the compounds of this invention. Depending on the specific gravity of the mineral oil, which should preferably be of a range from to 40 A.P.I., and on the particular specific gravity of the drilling emulsion which it is thus desired to obtain for a particular purpose, for example, for drilling through low pressure formations, the proportion in which oil is emulsified in water can be varied within fairly wide limits, although a ratio of about 25 to 50% by volume of the mineral oil to about 75 to 50% of water has been found to give especially favorable results.

Although in the above instances the present emulsions include only the three components described, that is, water, mineral oil and the emulsifying agent, various other components may be added thereto, if desired, for the purpose of controlling specific properties of the emulsions.

Thus, if it is desired to improve their plastering properties and thus to minimize the so-called filtering losses of the fluid to the formation, a blown asphalt can be added to the emulsion, and preferably to the mineral oil prior to emulsification, in relatively small quantities such as from 5 to on the weight of the mineral oil, as described in Patent No. 2,223,027.

If it is desired to give a greater consistency to the present emulsions and to increase their capacity for carrying drill cuttings, a finely-divided solid and preferably a colloidal material can be admixed with the emulsions, preferably during the emulsification process, to form a stable 36 three-phase emulsion. Thus bentonite may be added in amounts of from 1 to 5% by weight, or ordinary drilling clay in amounts from 1 to 40% by weight on the total weight of the emulsion.

Furthermore, the weight or specific gravity of the present emulsions can be accurately controlled by adding thereto, in a suitably comminuted form, any desired weighting material such as calcium carbonate, barytes, iron oxide, galena, etc. These materials have been found to remain stably suspended in the present emulsions while maintaining the specific gravity thereof within any desired range, such as from 67 to 120 lbs. per cubic foot.

Since the present emulsions are used on drilling installations wherein a drilling fluid of either the Waterbase or the oil-base type is usually already available, it has been found advantageous to apply the emulsifying agents of the present invention in forming drilling emulsions with these drilling fluids as starting material.

Thus, a water-base drilling fluid comprising water and clay and having a weight such, for example, as 86 lbs. per cubic foot, can be mixed with approximately 25 to 50% by volume of a heavy crude oil with the addition of 2.0 to 3.0% (calculated on the weight of the total mixture) of the instant compounds to give a stable emulsion having a weight of approximately 82 to 72 lbs. per cubic foot. 7

Likewise, an oil-base drilling fluid comprising, for example, crude oil or a diesel oil and calcium carbonate suspended therein by means -of agents such as tall oil and sodium silicate or hydroxide, as described in Patent No. 2,350,154 and having a weight such, for example, as 78 lbs. per cubic foot, may be mixed with approximately from one to three times its volume of water and emulsified therewith with the addition of the instant compounds to give a stable emulsion having a weight of approximately to 66 lbs. per cubic foot.

In this connection, it is especially important to note that the emulsifying action of the present compounds is not in any way impaired by the chemical compounds which are ordinarily used in controlling the viscosity, stability or other properties of such water-base or oil-base drilling fluids.

The drilling emulsions formed in the ways described hereinabove have the following advantages over waterbase and oil base drilling fluids; (1) they are considerably less expensive than oil-base drilling fluids so that drilling costs are greatly decreased; (2) their plastering properties are much superior to those of water-base drilling fluids and compare favorably with those of oil-base drilling fluids so that filtering losses to the formation are greatly minimized; (3) they are better adapted than oilbase drilling fluids for surveying wells by electrical logging methods; (4) greater drilling speeds can in general be realized with the drilling emulsions of the present type than with either water-base or oil-base drilling fluids.

The following examples are presented to illustrate the present invention.

Example Drilling emulsions are prepared by emulsifying a Ventura clay water base drilling fluid, treated with 0.3% by weight of sodium hexametaphosphate and weighing about 75 lbs. per cubic foot, with stove oil in the weight ratio of 75% Ventura drilling fluid, 22% Stove Oil and 3% emulsifier. The emulsifiers employed in producing these emulsions are shown in the following table. These emulsions are useful as drilling fluids.

Compounds used in emulsion fluids for drilling wells:

Polyethyleneimine, molecular weight 900 Polyethyleneimine, molecular weight 5,000 Polyethyleneimine, molecular weight 11,500 Polyethyleneimine, molecular weight 20,000 Polyethyleneimine, molecular weight 50,000 Polyethyleneimine, molecular weight 100,000

Polypropyleneimine, molecular weight 500 Polypropyleneimine, molecular weight 1,000 Polypropyleneimine, molecular weight 5,000 Polypropyleneimine, molecular weight 10,000 Polypropyleneimine, molecular weight 20,000 Polypropyleneimine, molecular weight 40,000

16-A 20A103 18-A3 45-O1A 19-A2 20-A102H 20 A 11-K 27-0 19-A3O1K 28-0 20-A1KA 29-0 10-U 32-0 12-U 37-0, s c, 45-0 12-c 47-0 51-O4AC 61 o 12-U3C 17-21 38 Having thus described our invention, what we claim as new and desire to obtain by Letters Patent is:

1. A drilling fluid for wells containing an emulsion of water and oil, a fine dispersed solid weighting material dispersed in said emulsion, and a minor amount of a linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms.

2. The drilling fluid of claim 1 wherein the linear 1O polymer of a 1,2-a1kyleneimine is polyethyleneimine.

3. The drilling fluid of claim 1 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

References Cited UNITED STATES PATENTS 2,182,306 12/1939 Ulrich e161. 260-2 2,272,489 2/1942 Ulrich 260-239 2,555,794 6/1951 Henkes 252 s.5 2,946,746 7/1960 Keller 252-s.5 2,999,063 9/1961 Hoeppel 2528.5

OTHER REFERENCES Schwartz-Perry: Surface Active Agents, p. 173, pub. 1949, by Interscience Publishers Inc. of New York.

LEON D. ROSDOL, Primary Examiner.

H. B. GUYNN, Assistant Examiner. 

1. A DRILLING FLUID FOR WELLS CONTAINING AN EMULSION OF WATER AND OIL, A FINE DISPERSED SOLID WEIGHTING MATERIAL DISPERSED IN SAID EMULSION, AND A MINOR AMOUNT OF A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS. 